Semi-crystalline polyamide composition with high glass transition temperature for thermoplastic material, process for manufacturing same and uses thereof

ABSTRACT

The invention relates to a composition for thermoplastic material comprising:
         0 to 70% by weight, preferentially 20% to 60% by weight, of short reinforcing fibers,   30% to 100% by weight, preferentially 40% to 80% by weight, of a thermoplastic matrix based on at least one semi-crystalline polyamide polymer,   0 to 50% of additives and/or other polymers,   said semi-crystalline polyamide polymer being:   a) a reactive composition comprising or consisting of at least one reactive polyamide prepolymer which is a precursor of said semi-crystalline polyamide polymer,   or, as an alternative to a),   b) a nonreactive composition of at least one polyamide polymer, said composition being that of said thermoplastic matrix defined above,   and said reactive polyamide prepolymer of the composition a) and said polyamide polymer of the composition b) comprising or consisting of at least one BACT/XT copolyamide.

The invention relates to a novel semi-crystalline (sc) polyamidecomposition having a high glass transition temperature, based onbis(aminomethyl)cyclohexane (BAC) for thermoplastic material.

It also relates to a process for manufacturing said thermoplasticmaterial and also the uses of said composition for manufacturingmechanical or structural parts based on said material for material partsand also the part which results therefrom and for applications in themotor vehicle, railway, marine, road transport, wind power, sport,aeronautical and aerospace, construction, panel and leisure fields.

A major challenge in materials is to find a polyamide resin which meetsthe following specifications:

-   -   High Tg for a wide range of operating temperatures;    -   The lowest possible Mp, so as to be readily processable without        recourse to excessively specific mold metallurgies;    -   A very good crystallization capacity in order to be able to be        rapidly demolded and thus to be compatible with intensive        production cycles, such as those used in the motor vehicle        industry;    -   A high rigidity, including under hot conditions, so as to be        able to obtain the highest possible moduli of the final        material.

Document CN104211953 describes a polyamide composition comprising from30% to 99.9% by weight of a polyamide resin comprising from 60 to 95 mol% of 10T, from 5 to 40 mol % of 5′T, 5′ corresponding to2-methyl-1,5-pentamethylenediamine, from 0% to 70% by weight of areinforcing filler and from 0.1% to 50% by weight of an additive.

The polyamide resin has a melting point above 260° C.

EP 550 314 describes, among its examples, (nonreactive) copolyamidecompositions in a search for melting points of greater than 250° C. andlimited Tg values, with the majority of the examples cited having anexcessively low Tg (<80° C.) or an excessively high Mp (>300° C.).

EP 1 988 113 describes a molding composition based on a 10T/6Tcopolyamide with:

-   -   40 to 95 mol % of 10T    -   5 to 40% of 6T.

Polyamides with a high melting point of greater than 270° C. aretargeted in particular. The examples mentioned and FIG. 1 teach that themelting point of these compositions is at least approximately 280° C.

WO 2011/003973 describes compositions comprising from 50 mol % to 95 mol% of a unit based on a linear aliphatic diamine comprising from 9 to 12carbon atoms and on terephthalic acid and from 5% to 50% of unitcombining terephthalic acid with a mixture of 2,2,4- and2,4,4-trimethylhexanediamine.

US 2011/306718 describes a process for the pultrusion of reactivealiphatic polyamides having low Tg values in combination with chainextenders of polymeric structure bearing several (and many more than 2)anhydride or epoxide functions. This document does not describe anynonpolymeric extender.

WO 2014/064375 describes in particular a PA MXDT/10T which exhibits anexcellent compromise between the various characteristics describedabove. Unfortunately, the meta-xylene diamine (MXD) monomer used ishighly subject to side-reactions, giving rise in particular to theformation of branching.

The drawbacks of the prior art, with the absence of a good compromisebetween the mechanical performance levels and the processing ability(ease of transformation) at lower temperature with a shorter productioncycle time are overcome by means of the solution of the presentinvention which targets semi-crystalline PA compositions having anexcellent compromise between high mechanical performance levels(mechanical strength), in particular under hot conditions, and easyprocessing. It in fact has a high rigidity and has a glass transitiontemperature >120° C., a Mp<290° C., and also an excellentcrystallization capacity (Mp−Tc<40° C.), which makes it a matrix ofchoice for extrusion, injection-molding or molding processing, inparticular for the wind power, motor vehicle or aeronautical industry.

More particularly, in the case of the reactive compositions, it issought to have faster reaction kinetics while at the same time having arate and/or temperature of crystallization of the polymer formed thatare also higher.

The choice of a semi-crystalline polyamide polymer, as matrix of thethermoplastic material of the invention, has the advantage, comparedwith amorphous polyamides, of significantly improved mechanicalperformance levels, especially at elevated temperature, such as creepresistance or fatigue resistance. In addition, having a melting pointabove 200° C. has the advantage in the motor vehicle industry of beingcompatible with treatments by cataphoresis, which a structure ofamorphous PA type does not permit. As for the amorphous materials, a Tgof greater than or equal to 90° C. is sought so as to ensure goodmechanical properties for the thermoplastic material over the entireworking temperature range, for example up to 90° C. for the wind powerindustry, up to 100° C. for the motor vehicle industry and up to 120° C.for the aeronautical industry. Conversely, an excessively high meltingpoint, in particular of greater than 290° C., is on the other handharmful as it requires processing the thermoplastic material at highertemperatures with constraints in terms of molding equipment to be used(and associated heating system) and excessive consumption of energywith, in addition, risks of thermal degradation due to heating attemperatures higher than the melting point of said polyamide, with as aconsequence the modification of the properties of the finalthermoplastic matrix and of the material which results therefrom. Thecrystallinity of said polymer must be as high as possible, but with amelting point Mp that is not too high (Mp<290° C. and more particularly<280° C.) in order to optimize the mechanical performance levels and thecrystallization rate and/or the crystallization temperature must be ashigh as possible, in order to reduce the molding time before ejection ofthe molded part with a selective choice of the composition of saidsemi-crystalline polyamide.

The subject of the present invention is the processing of novel specificcompositions of thermoplastic material, in particular based onsemi-crystalline polyamide, having a good compromise between highmechanical performance levels (mechanical strength), in particular hotmechanical performance levels, and easy processing. This means that theobjective is compositions that are easy to process with transformationand processing temperatures that are lower than those for othercompositions of the prior art, with a more favorable overall processingenergy balance, a shorter cycle time and a higher productivity. Moreparticularly, the solution of the invention, in the case of reactivecompositions, allows, using compositions based on semi-crystallinereactive polyamide prepolymers, both fast reaction kinetics and fastcrystallization kinetics with a shorter cycle time. More particularly,the polyamide polymer matrix, while having a high Tg and a limited Mp,as defined, with easy processing of said thermoplastic material, mustalso have a high crystallization speed characterized first by adifference between melting point and crystallization temperature Mp−Tcnot exceeding 40° C., preferably not exceeding 30° C. Consequently, theobject of the invention is to develop a polyamide compositioncorresponding to the needs already defined above:

-   -   High Tg for a wide range of operating temperatures;    -   The lowest possible Mp, so as to be readily processable without        recourse to excessively specific mold metallurgies;    -   A very good crystallization capacity in order to be able to be        rapidly demolded and thus to be compatible with intensive        production cycles, such as those used in the motor vehicle        industry;    -   A high rigidity, including under hot conditions, so as to be        able to obtain the highest possible moduli of the final        material.

The present invention relates to a composition for thermoplasticmaterial comprising:

-   -   0 to 70% by weight, preferentially 20% to 60% by weight, of        short reinforcing fibers,    -   30% to 100% by weight, preferentially 40% to 80% by weight, of a        thermoplastic matrix based on at least one semi-crystalline        polyamide polymer,    -   0 to 50% of additives and/or other polymers,

said semi-crystalline polyamide polymer being:

a) a reactive composition comprising or consisting of at least onereactive polyamide prepolymer which is a precursor of saidsemi-crystalline polyamide polymer,

or, as an alternative to a),

b) a nonreactive composition of at least one polyamide polymer, saidcomposition being that of said thermoplastic matrix defined above,

and said reactive polyamide prepolymer of the composition a) and saidpolyamide polymer of the composition b) comprising or consisting of atleast one BACT/XT copolyamide in which:

-   -   BACT is a unit comprising an amide unit present at a molar        content ranging from 20% to 70%, preferably from 25% to 60%,        more preferentially from 35% to 55%, wherein BAC is chosen from        1,3-bis(aminomethyl)cyclohexyl (1,3-BAC),        1,4-bis(aminomethyl)cyclohexyl (1,4-BAC) and a mixture thereof,        and T is terephthalic acid,    -   XT is a unit comprising an amide unit present at a molar content        ranging from 30% to 80%, preferably from 40% to 75%, more        preferentially from 45% to 65%, wherein X is a C9 to C18,        preferably C9, C10, C11 and C12, preferentially C10, C11 and        C12, linear aliphatic diamine, and wherein T is terephthalic        acid;    -   in the BACT and/or XT units, independently of one another, up to        30 mol %, preferably 20 mol %, in particular up to 10 mol %,        relative to the total amount of dicarboxylic acids, of the        terephthalic acid can be replaced with other aromatic, aliphatic        or cycloaliphatic dicarboxylic acids comprising 6 to 36 carbon        atoms, in particular 6 to 14 carbon atoms, and    -   in the BACT and/or XT units, independently of one another, up to        30 mol %, preferably 20 mol %, in particular up to 10 mol %, of        the BAC and/or where appropriate of X, relative to the total        amount of diamines, can be replaced with other diamines        comprising from 4 to 36 carbon atoms, in particular 6 to 12        carbon atoms, and    -   in the copolyamide, no more than 30 mol %, preferably no more        than 20 mol %, preferably no more than 10 mol %, relative to the        total amount of monomers, can be formed by lactams or        aminocarboxylic acids, and    -   on condition that the sum of the monomers which replace the        terephthalic acid, the BAC and X does not exceed a concentration        of 30 mol %, preferably 20 mol %, preferably 10 mol %, relative        to the total amount of monomers used in the copolyamide, and    -   on condition that BACT and XT units are always present in said        polyamide polymer.

Said semi-crystalline polyamide polymer is consequently thesemi-crystalline polyamide polymer which forms the basis of thethermoplastic matrix, said thermoplastic matrix possibly being obtainedfrom the reactive composition a) which corresponds to:

either a polyamide prepolymer with a di-NH₂ or di-CO₂H end group whichcan react respectively with another polyamide prepolymer with a di-CO₂Hor di-NH₂ end group to give said semi-crystalline polyamide polymer,

or a prepolymer with an NH₂ and CO₂H end group which can react withitself, to give said semi-crystalline polyamide polymer,

or a prepolymer which can react with a chain extender, to give saidsemi-crystalline polyamide polymer,

or the semi-crystalline polyamide polymer is already present in thenon-reactive composition b).

In other words, the present invention relates to a composition forthermoplastic material comprising:

-   -   0 to 70% by weight, preferentially 20% to 60% by weight, of        short reinforcing fibers,    -   30% to 100% by weight, preferentially 40% to 80% by weight, of a        thermoplastic matrix based on at least one semi-crystalline        polyamide polymer,    -   0 to 50% of additives and/or other polymers,

said thermoplastic matrix being:

a) a reactive composition comprising or consisting of at least onereactive polyamide prepolymer which is a precursor of saidsemi-crystalline polyamide polymer,

or, as an alternative to a),

b) a nonreactive composition of at least one polyamide polymer, saidcomposition being that of said thermoplastic matrix defined above,

and said reactive polyamide prepolymer of the composition a) and saidpolyamide polymer of the composition b) comprising or consisting of atleast one BACT/XT copolyamide in which:

-   -   BACT is a unit comprising an amide unit present at a molar        content ranging from 20% to 70%, preferably from 25% to 60%,        more preferentially from 35% to 55%, wherein BAC is chosen from        1,3-bis(aminomethyl)cyclohexyl (1,3-BAC) and        1,4-bis(aminomethyl)cyclohexyl (1,4-BAC) and a mixture thereof,        and T is terephthalic acid,    -   XT is a unit comprising an amide unit present at a molar content        ranging from 30% to 80%, preferably from 40% to 75%, more        preferentially from 45% to 65%, wherein X is a C₉ to C₁₈,        preferably C₉, C₁₀, C₁₁, and C₁₂, preferentially C₁₀, C₁₁ and        C₁₂, linear aliphatic diamine, and wherein T is terephthalic        acid;    -   in the BACT and/or XT units, independently of one another, up to        30 mol %, preferably 20 mol %, in particular up to 10 mol %,        relative to the total amount of dicarboxylic acids, of the        terephthalic acid can be replaced with other aromatic, aliphatic        or cycloaliphatic dicarboxylic acids comprising 6 to 36 carbon        atoms, in particular 6 to 14 carbon atoms, and    -   in the BACT and/or XT units, independently of one another, up to        30 mol %, preferably 20 mol %, in particular up to 10 mol %, of        the BAC and/or where appropriate of X, relative to the total        amount of diamines, can be replaced with other diamines        comprising from 4 to 36 carbon atoms, in particular 6 to 12        carbon atoms, and    -   in the copolyamide, no more than 30 mol %, preferably no more        than 10 mol %, relative to the total amount of monomers, can be        formed by lactams or aminocarboxylic acids, and    -   on condition that the sum of the monomers which replace the        terephthalic acid, the BAC and X does not exceed a concentration        of 30 mol %, preferably 10 mol %, relative to the total amount        of monomers used in the copolyamide, and    -   on condition that BACT and XT units are always present in said        polyamide polymer.

The expression “said reactive polyamide prepolymer of the composition a)and said polyamide polymer of the composition b) comprising orconsisting of at least one BACT/XT copolyamide” signifies that thereactive polyamide prepolymer of the composition a) or said polyamidepolymer of the composition b) consist exclusively of units comprisingBACT and XT amide units in respective proportions defined above, or thereactive polyamide prepolymer of the composition a) or said polyamidepolymer of the composition b) comprise BACT and XT amide units inrespective proportions defined above, but also other units comprisingamide units.

Advantageously, the proportion of units comprising amide units theproportion of BACT/XT BACT and XT in the reactive polyamide prepolymerof the composition a) or said polyamide polymer of the composition b) isgreater than 50%, in particular greater than 60%, in particular greaterthan 70%, preferentially greater than 80%, in particular greater than90%.

The present invention therefore relates to a composition forthermoplastic material comprising:

-   -   0 to 70% by weight, preferentially 20% to 60% by weight, of        short reinforcing fibers,    -   30% to 100% by weight, preferentially 40% to 80% by weight, of a        thermoplastic matrix based on at least one semi-crystalline        polyamide polymer,    -   0 to 50% of additives and/or other polymers,

said semi-crystalline polyamide polymer comprising or consisting of atleast one BACT/XT copolyamide in which:

-   -   BACT is a unit comprising an amide unit present at a molar        content ranging from 20% to 70%, preferably from 25% to 60%,        more preferentially from 35% to 55%, wherein BAC is chosen from        1,3-bis(aminomethyl)cyclohexyl (1,3-BAC),        1,4-bis(aminomethyl)cyclohexyl (1,4-BAC) and a mixture thereof,        and T is terephthalic acid,    -   XT is a unit comprising an amide unit present at a molar content        ranging from 30% to 80%, preferably from 40% to 75%, more        preferentially from 45% to 65%, wherein X is a C₉ to C₁₈,        preferably C₉, C₁₀, C₁₁ and C₁₂, preferentially C₁₀, C₁₁, and        C₁₂, linear aliphatic diamine, and wherein T is terephthalic        acid;    -   in the BACT and/or XT units, independently of one another, up to        30 mol %, preferably 20 mol %, in particular up to 10 mol %,        relative to the total amount of dicarboxylic acids, of the        terephthalic acid can be replaced with other aromatic, aliphatic        or cycloaliphatic dicarboxylic acids comprising 6 to 36 carbon        atoms, in particular 6 to 14 carbon atoms, and    -   in the BACT and/or XT units, independently of one another, up to        30 mol %, preferably 20 mol %, in particular up to 10 mol %, of        the BAC and/or where appropriate of X, relative to the total        amount of diamines, can be replaced with other diamines        comprising from 4 to 36 carbon atoms, in particular 6 to 12        carbon atoms, and    -   in the copolyamide, no more than 30 mol %, preferably no more        than 10 mol %, relative to the total amount of monomers, can be        formed by lactams or aminocarboxylic acids, and    -   on condition that the sum of the monomers which replace the        terephthalic acid, the BAC and X does not exceed a concentration        of 30 mol %, preferably 10 mol %, relative to the total amount        of monomers used in the copolyamide, and

on condition that BACT and XT units are always present in said polyamidepolymer.

The composition according to the invention can comprise shortreinforcing fibers (or short fibrous reinforcement).

Preferably, the “short” fibers are between 200 and 400 μm in length.

These short reinforcing fibers may be chosen from:

-   -   natural fibers;    -   mineral fibers, said fibers having high melting points Mp′ above        the melting point Mp of said semi-crystalline polyamide of the        invention and above the polymerization and/or processing        temperature;    -   polymeric fibers or polymer fibers having a melting point Mp′,        or if not Mp′, a glass transition temperature Tg′, above the        polymerization temperature or above the melting point Mp of said        semi-crystalline polyamide constituting said matrix of the        thermoplastic material and above the processing temperature;    -   or mixtures of the abovementioned fibers.

As mineral fibers suitable for the invention, mention may be made ofcarbon fibers, which include fibers of nanotubes or carbon nanotubes(CNTs), carbon nanofibers or graphenes; silica fibers such as glassfibers, in particular of E, R or S2 type; boron fibers; ceramic fibers,in particular silicon carbide fibers, boron carbide fibers, boroncarbonitride fibers, silicon nitride fibers, boron nitride fibers,basalt fibers; fibers or filaments based on metals and/or alloysthereof; fibers of metal oxides, in particular of alumina (Al₂O₃);metallized fibers such as metallized glass fibers and metallized carbonfibers, or mixtures of the abovementioned fibers.

More particularly, these fibers may be chosen as follows:

-   -   the mineral fibers may be chosen from: carbon fibers, carbon        nanotube fibers, glass fibers, in particular of E, R or S2 type,        boron fibers, ceramic fibers, in particular silicon carbide        fibers, boron carbide fibers, boron carbonitride fibers, silicon        nitride fibers, boron nitride fibers, basalt fibers, fibers or        filaments based on metals and/or alloys thereof, fibers based on        metal oxides such as Al₂O₃, metallized fibers such as metallized        glass fibers and metallized carbon fibers, or mixtures of the        abovementioned fibers, and    -   the polymer fibers or polymeric fibers, under the abovementioned        condition, are chosen from:    -   thermosetting polymer fibers and more particularly those chosen        from: unsaturated polyesters, epoxy resins, vinyl esters,        phenolic resins, polyurethanes, cyanoacrylates and polyimides,        such as bismaleimide resins, or aminoplasts resulting from the        reaction of an amine such as melamine with an aldehyde such as        glyoxal or formaldehyde,    -   fibers of thermoplastic polymers, more particularly chosen from:        polyethylene terephthalate (PET), polybutylene terephthalate        (PBT),    -   polyamides fibers,    -   fibers of aramids (such as Kevlar®) and aromatic polyamides such        as those corresponding to one of the formulae: PPD.T, MPD.I, PAA        and PPA, with PPD and MPD being respectively p- and        m-phenylenediamine, PAA being polyarylamides and PPA being        polyphthalamides,    -   fibers of polyamide block copolymers such as        polyamide/polyether, fibers of polyaryl ether ketones (PAEKs)        such as polyether ether ketone (PEEK), polyether ketone ketone        (PEKK) or polyether ketone ether ketone ketone (PEKEKK).

The preferred short reinforcing fibers are short fibers (with a circularcross-section) chosen from: carbon fibers, including those which aremetallized, glass fibers, including those which are metallized, of E, R,S2 type, fibers of aramids (such as Kevlar®) or aromatic polyamides,polyaryl ether ketone (PAEK) fibers, such as polyether ether ketone(PEEK) fibers, polyether ketone ketone (PEKK) fibers, polyether ketoneether ketone ketone (PEKEKK) fibers, or mixtures thereof.

More particularly, the natural fibers are chosen from linseed, castor,wood, sisal, kenaf, coconut, hemp and jute fibers.

Preferably, the reinforcing fibers present in the composition accordingto the invention are chosen from glass fibers, carbon fibers, fromlinseed fibers and mixtures thereof, and more preferentially linseedfibers and carbon fibers, and even more preferentially carbon fibers.

With regard to the additives, without being limited thereto, thecomposition according to one preferred variant of the invention moreparticularly comprises specific additives such as heat stabilizers, inparticular these stabilizers are antioxidants against thermo-oxidationand/or photo-oxidation of the polymer of the thermoplastic matrix andare organic or inorganic stabilizers.

The expression “organic stabilizer” or more generally a “combination oforganic stabilizers” denotes a primary antioxidant of phenol type, asecondary antioxidant of phosphite type and even optionally otherstabilizers, such as a HALS, which means Hindered Amine Light Stabilizer(for example Tinuvin® 770 from the company Ciba), an anti-UV agent (forexample Tinuvin® 312 from the company Ciba), a phenolic stabilizer or aphosphorus-based stabilizer. Use may also be made of antioxidants ofamine type, such as Naugard® 445 from the company Crompton, or elsepolyfunctional stabilizers, such as Nylostab® S-EED from the companyClariant.

The organic stabilizer present can be chosen, without this list beingrestrictive, from:

-   -   phenolic antioxidants, for example Irganox® 245, Irganox® 1010        or Irganox® 1098 from the company Ciba, Irganox® MD1024 from the        company Ciba, Lowinox® 44B25 from the company Great Lakes, or        ADK® Stab AO-80 from the company Adeka Palmarole,    -   phosphorus-based stabilizers, such as phosphites, for example        Irgafos® 168 from the company Ciba,    -   a UV absorber, such as Tinuvin® 312 from the company Ciba,    -   a HALS, as previously mentioned,    -   a stabilizer of amine type, such as Naugard® 445 from the        company Crompton, or else of hindered amine type, such as        Tinuvin® 770 from the company Ciba,    -   a polyfunctional stabilizer, such as Nylostab® S-EED from the        company Clariant.

A mixture of two, or more, of these organic stabilizers can of course beenvisioned.

The expression “inorganic stabilizer” denotes a copper-based stabilizer.By way of example of such inorganic stabilizers, mention may be made ofcopper halides and copper acetates. Secondarily, other metals such assilver can optionally be considered, but these metals are known to beless effective. These copper-based compounds are typically combined withhalides of alkali metals, in particular potassium.

These inorganic stabilizers are more particularly used, when thestructures must have improved long-term heat resistance in hot air, inparticular for temperatures of greater than or equal to 100-120° C.,since they tend to prevent polymer-chain cleavages.

More particularly, the term “copper-based stabilizer” is intended tomean a compound comprising at least one copper atom, in particular inionic or ionizable form, for example in the form of a complex.

The copper-based stabilizer can be chosen from cuprous chloride, cupricchloride, cuprous bromide, cupric bromide, cuprous iodide, cupriciodide, cuprous acetate and cupric acetate. Mention may be made ofhalides and acetates of other metals, such as silver, in combinationwith the copper-based stabilizer. These copper-based compounds aretypically combined with alkali metal halides. A well-known example isthe mixture of CuI and KI, where the CuI:KI ratio is typically between1:5 and 1:15. An example of such a stabilizer is Polyadd P201 from thecompany Ciba.

Further details on copper-based stabilizers will be found in U.S. Pat.No. 2,705,227. More recently, copper-based stabilizers such as complexedcoppers, for instance Bruggolen H3336, H3337 or H3373 from the companyBrüggemann, have emerged.

Advantageously, the copper-based stabilizer is chosen from copperhalides, copper acetate, copper halides or copper acetate as a mixturewith at least one alkali metal halide, and mixtures thereof, preferablymixtures of copper iodide and of potassium iodide (CuI/KI).

The additive can also be an impact modifier, advantageously consistingof a polymer having a flexural modulus of less than 100 MPa, measuredaccording to the standard ISO 178 and with a Tg of less than 0° C.(measured according to the standard 11357-2:2013 at the inflection pointof the DSC thermogram), in particular a polyolefin, optionally coupledwith a Peba, having a flexural modulus <200 MPa.

The polyolefin of the impact modifier can be functionalized ornon-functionalized or can be a mixture of at least one functionalizedand/or of at least one non-functionalized.

The additives can also be fillers which can in particular be any fillerknown to those skilled in the art in the field of thermoplasticmaterials. They may in particular be heat-conducting and/or electricallyconductive fillers, such as metal powder, pulverulent carbon black,carbon fibrils, carbon nanotubes (CNTs), silicon carbide, boroncarbonitride, boron nitride or silicone nitride. In this respect,reference may be made to application WO 2010/130930 by the applicant.

The reinforcing fibers, whether they are long, short or continuous, areexcluded from the additives and in particular the term “inorganicfiller” excludes the long, short or continuous reinforcing fibers.

The additives may also be flame retardants, such as a metal salt chosenfrom a metal salt of phosphinic acid, a metal salt of diphosphinic acid,a polymer containing at least one metal salt of phosphinic acid, and apolymer containing at least one metal salt of diphosphinic acid.

Advantageously, the additive is chosen from an antioxidant, a heatstabilizer, a UV absorber, a light stabilizer, an impact modifier, alubricant, an inorganic filler, a flame retardant agent, a nucleatingagent and a dye.

The expression “other polymers” denotes any thermoplastic polymer and inparticular a polyamide polymer, in particular an aliphatic,cycloaliphatic or aromatic polyamide, which may be microcrystalline oramorphous.

The expression “non-reactive composition” means that the composition isbased on polyamide polymer in which the molecular weight is not capableof changing during its processing and which therefore corresponds to thefinal polyamide polymer of the thermoplastic matrix.

These polyamides according to composition b) are nonreactive, eitherbecause of the low content of reactive (residual) functions present, inparticular with a content of said functions <120 meq/kg, or because ofthe presence of end functions of the same type at the chain end whichare therefore nonreactive with one another, or because of themodification and blocking of said reactive functions by a monofunctionalreactive component, for example, for the amine functions, by amodification reaction with a monoacid or a monoisocyanate and, forcarboxyl functions, by reaction with a monoamine.

Advantageously, the number-average molecular weight (Mn) of said finalpolyamide polymer of the thermoplastic matrix of said material ispreferably in a range of from 8000 to 40 000 g/mol, preferably from 10000 to 30 000 g/mol, as determined by calculation on the basis of thecontent of end functions, determined by potentiometric titration insolution and the functionality of said prepolymers or by NMR. These Mnvalues can correspond to inherent viscosities greater than or equal to0.8, as determined according to the standard ISO 307:2007, but changingthe solvent (use of m-cresol in place of sulfuric acid and thetemperature being 20° C.).

Conversely, the expression “reactive composition” means that themolecular weight of said reactive composition will change duringprocessing by reaction of reactive prepolymers with one another bycondensation, or with a chain extender by polyaddition and withoutelimination of volatile by-products, so as to give the final polyamidepolymer of the thermoplastic matrix.

1,3-BAC (or 1,3-bis(aminomethyl)cyclohexane, CAS No. 2579-20-6) is acycloaliphatic diamine monomer obtained in particular by hydrogenationof meta-xylenediamine (MXDA). 1,3-BAC exists in the form of two isomers,cis and trans, CAS No. 2579-20-6 corresponding to a mixture of isomers.

1,4-BAC (or 1,4-bis(aminomethyl)cyclohexane, CAS No. 2549-07-9) is acycloaliphatic diamine monomer obtained in particular by hydrogenationof para-xylenediamine (PXDA). 1,4-BAC exists in the form of two isomers,cis and trans, CAS No. 2549-07-9 corresponding to a mixture of isomers.

Advantageously, the 1,3-BAC or the 1,4-BAC used in the BACT unit is amixture of cis and trans isomers in a respective proportion of from0/100 to 100/0, in particular from 75/25 to 25/75.

Advantageously, the proportion of cis-isomer in the 1,3-BAC is greaterthan 60%, preferentially greater than 70%, in particular greater than80%, in particular greater than 90%.

Advantageously, the proportion of trans-isomer in the 1,4-BAC is greaterthan 60%, preferentially greater than 70%, in particular greater than80%, in particular greater than 90%.

BAC and/or X can be replaced, independently of one another, up to 30 mol%, by other diamines defined above, in particular by a linear orbranched aliphatic diamine, a cycloaliphatic diamine or an arylaromaticdiamine such as meta-xylenediamine (MXDA).

By way of example, the linear or branched aliphatic diamine is chosenfrom 1,4-butanediamine, 1,5-pentanediamine, 2-methyl-1,5-pentanediamine(MPMD), 1,6 hexanediamine, 1,8-octanediamine (OMDA), 1,9-nonanediamine(NMDA), 2-methyl-1,8-octanediamine (MODA),2,2,4-trimethylhexamethylenediamine (TMHMD),2,4,4-trimethylhexamethylenediamine (TMHMD), 5-methyl-1,9-nonanediamine,1,11-undecanediamine, 2-butyl-2-ethyl-1,5-pentanediamine,1,12-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine,1,16-hexadecanediamine and 1,18-octadecanediamine.

The cycloaliphatic diamine can be chosen from isophoronediamine,norbornanedimethylamine, 4,4′-diaminodicyclohexylmethane (PACM),2,2-(4,4′-diaminodicyclohexyl)propane (PACP), and3,3′-dimethyl-4,4′-diaminodicyclohexylethane (MACM).

T can be replaced, up to 30 mol %, by other dicarboxylic acids definedabove, in particular by other aromatic, aliphatic or cycloaliphaticdicarboxylic acids.

The aromatic dicarboxylic acids can be chosen fromnaphthalenedicarboxylic acid (NDA) and isophthalic acid (IPS).

The aliphatic dicarboxylic acids can be chosen from adipic acid, subericacid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioicacid, brassylic acid, tetradecanedioic acid, pentadecanedioic acid,hexadecanedioic acid, octadecanedioic acid and dimerized fatty acids.

The cycloaliphatic dicarboxylic acids can be chosen from cis- and/ortrans-cyclohexane-1,4-dicarboxylic acid and/or cis- and/ortrans-cyclohexane-1,3-dicarboxylic acid (CHDA).

BAC and/or X and/or T can be replaced, independently of one another, upto 30 mol %, by lactams or aminocarboxylic acids.

The lactams and aminocarboxylic acids can be chosen from caprolactam(CL), α,ω-aminocaproic acid, α,ω-aminononanoic acid, α,ω-aminoundecanoicacid (AUA), lauryllactam (LL) and α,ω-aminododecanoic acid (ADA).

A maximum of 30 mol %, relative to the total sum of the BAC, X and Tmonomers, of replacement, whether it is with another diamine, anotherdiacid, a lactam or an aminocarboxylic acid, or any mixture thereof, ispossible.

Advantageously, a maximum of 20 mol %, relative to the total sum of theBAC, X and T monomers, of replacement, whether it is with anotherdiamine, another diacid, a lactam or an aminocarboxylic acid, or anymixture thereof, is possible.

Advantageously, a maximum of 10 mol %, relative to the total sum of theBAC, X and T monomers, of replacement, whether it is with anotherdiamine, another diacid, a lactam or an aminocarboxylic acid, or anymixture thereof, is possible.

In one advantageous embodiment, the present invention relates to one ofthe compositions for thermoplastic material Nos. 1 to 12 defined below,said composition comprising a semi-crystalline polyamide polymer andoptionally short reinforcing fibers, said semi-crystalline polyamidepolymer comprising a BACT/XT copolyamide in the proportions defined intable I below:

TABLE I Semi- crystalline Short polyamide reinforcing polymer fibersComposition % by % by BACT XT No. weight weight mol % mol %  1  30-100 0-70 20-70 30-80  2  30-100  0-70 25-60 40-75  3  30-100  0-70 35-5545-65  4 40-80  0-70 20-70 30-80  5 40-80  0-70 25-60 40-75  6 40-80 0-70 35-55 45-65  7  30-100 20-60 20-70 30-80  8  30-100 20-60 25-6040-75  9  30-100 20-60 35-55 45-65 10 40-80 20-60 20-70 30-80 11 40-8020-60 25-60 40-75 12 40-80 20-60 35-55 45-65

Advantageously, compositions 1 to 12 comprise from 0% to 50% by weightof additives and/or of other polymers.

Advantageously, said compositions consist of a semi-crystallinepolyamide polymer, optionally of short reinforcing fibers, and of 0% to50% by weight of additives and/or of other polymers, saidsemi-crystalline polyamide polymer comprising a BACT/XT copolyamide inthe proportions defined in table I.

Advantageously, said compositions consist of a semi-crystallinepolyamide polymer, optionally of short reinforcing fibers, and of 0% to50% by weight of additives and/or of other polymers, saidsemi-crystalline polyamide polymer consisting of a BACT/XT copolyamidein the proportions defined in table I.

Advantageously, the proportion of additives and/or of other polymers inthe compositions defined above is in addition from 0% to 50% by weight.

Advantageously, in the compositions defined above, X is a C₉, C₁₀, C₁₁and C₁₂, in particular C₁₀, C₁₁ and C₁₂, diamine.

The inventors have therefore found, unexpectedly, that the compositionsof the invention exhibit a better crystallization capacity, a betterhigh Tg/low Mp compromise and especially a higher enthalpy (andtherefore higher hot modulus) than the prior art compositions.

In one advantageous embodiment, the present invention relates to acomposition as defined above, in which said semi-crystalline polyamidepolymer has a melting point Mp<290° C., preferably <285° C., morepreferentially <280° C., as determined according to the standard ISO11357-3 (2013).

In one advantageous embodiment, the present invention relates to acomposition as defined above, in which said semi-crystalline polyamidepolymer has a glass transition temperature Tg>120° C., preferably >130°C., more preferentially >140° C., determined according to the standardISO 11357-2:2013.

Advantageously, the Tg is between 125 and 165° C.

In one advantageous embodiment, the present invention relates to acomposition as defined above, in which said semi-crystalline polyamidepolymer exhibits a difference between the melting point and thecrystallization temperature Mp−Tc<40° C., preferably <30° C., determinedaccording to the standard ISO 11357-3:2013.

In one advantageous embodiment, the present invention relates to acomposition as defined above, characterized in that the heat ofcrystallization of the semi-crystalline polyamide polymer, measured bydifferential scanning calorimetry (DSC) according to the standard ISO11357-3:2013, is greater than 40 J/g, preferably greater than 45 J/g,and even more preferentially 50 J/g.

In one advantageous embodiment, the present invention relates to acomposition as defined above, characterized in that saidsemi-crystalline polyamide polymer has a melting point: Mp<290° C. and aTg>120° C.

In one advantageous embodiment, the present invention relates to acomposition as defined above, characterized in that saidsemi-crystalline polyamide polymer has a melting point: Mp<290° C. and aTg>130° C.

In one advantageous embodiment, the present invention relates to acomposition as defined above, characterized in that saidsemi-crystalline polyamide polymer has a melting point: Mp<290° C. and aTg>140° C.

In one advantageous embodiment, the present invention relates to acomposition as defined above, characterized in that saidsemi-crystalline polyamide polymer has a melting point: Mp<285° C. and aTg>120° C.

In one advantageous embodiment, the present invention relates to acomposition as defined above, characterized in that saidsemi-crystalline polyamide polymer has a melting point: Mp<285° C. and aTg>130° C.

In one advantageous embodiment, the present invention relates to acomposition as defined above, characterized in that saidsemi-crystalline polyamide polymer has a melting point: Mp<285° C. and aTg>140° C.

In one advantageous embodiment, the present invention relates to acomposition as defined above, characterized in that saidsemi-crystalline polyamide polymer has a melting point: Mp<280° C. and aTg>120° C.

In one advantageous embodiment, the present invention relates to acomposition as defined above, characterized in that saidsemi-crystalline polyamide polymer has a melting point: Mp<280° C. and aTg>130° C.

In one advantageous embodiment, the present invention relates to acomposition as defined above, characterized in that saidsemi-crystalline polyamide polymer has a melting point: Mp<280° C. and aTg>140° C.

In one advantageous embodiment, the present invention relates to acomposition as defined above, characterized in that saidsemi-crystalline polyamide polymer has the following characteristics(table II):

TABLE II Compostion Initial Mp Tg Mp- Delta No. compositions (° C.) (°C.) Tc (° C.) Hc (J/g) 13 Compositions <290 >120° C. 1 to 12 14Compositions <290 >130° C. 1 to 12 15 Compositions <290 >140° C. 1 to 1216 Compositions <285 >120° C. 1 to 12 17 Compositions <285 >130° C. 1 to12 18 Compositions <285 >140° C. 1 to 12 19 Compositions <280 >120° C. 1to 12 20 Compositions <280 >130° C. 1 to 12 21 Compositions <280 >140°C. 1 to 12 22 Compositions <290 >120° C. <40 1 to 12 23 Compositions<290 >130° C. <40 1 to 12 24 Compositions <290 >140° C. <40 1 to 12 25Compositions <285 >120° C. <40 1 to 12 26 Compositions <285 >130° C. <401 to 12 27 Compositions <285 >140° C. <40 1 to 12 28 Compositions<280 >120° C. <40 1to 12 29 Compositions <280 >130° C. <40 1 to 12 30Compositions <280 >140° C. <40 1 to 12 31 Compositions <290 >120° C. <301 to 12 32 Compositions <290 >130° C. <30 1 to 12 33 Compositions<290 >140° C. <30 1 to 12 34 Compositions <285 >120° C. <30 1 to 12 35Compositions <285 >130° C. <30 1 to 12 36 Compositions <285 >140° C. <301 to 12 37 Compositions <280 >120° C. <30 1 to 12 38 Compositions<280 >130° C. <30 1 to 12 39 Compositions <280 >140° C. <30 1 to 12 40Compositions <290 >120° C. <40 >40 1 to 12 41 Compositions <290 >130° C.<40 >40 1 to 12 42 Compositions <290 >140° C. <40 >40 1 to 12 43Compositions <285 >120° C. <40 >40 1 to 12 44 Compositions <285 >130° C.<40 >40 1 to 12 45 Compositions <285 >140° C. <40 >40 1 to 12 46Compositions <280 >120° C. <40 >40 1 to 12 47 Compositions <280 >130° C.<40 >40 1 to 12 48 Compositions <280 >140° C. <40 >40 1 to 12 49Compositions <290 >120° C. <30 >40 1 to 12 50 Compositions <290 >130° C.<30 >40 1 to 12 51 Compositions <290 >140° C. <30 >40 1 to 12 52Compositions <285 >120° C. <30 >40 1 to 12 53 Compositions <285 >130° C.<30 >40 1 to 12 54 Compositions <285 >140° C. <30 >40 1 to 12 55Compositions <280 >120° C. <30 >40 1 to 12 56 Compositions <280 >130° C.<30 >40 1 to 12 57 Compositions <280 >140° C. <30 >40 1 to 12 58Compositions <290 >120° C. <40 >45 1 to 12 59 Compositions <290 >130° C.<40 >45 1 to 12 60 Compositions <290 >140° C. <40 >45 1 to 12 61Compositions <285 >120° C. <40 >45 1 to 12 62 Compositions <285 >130° C.<40 >45 1 to 12 63 Compositions <285 >140° C. <40 >45 1 to 12 64Compositions <280 >120° C. <40 >45 1 to 12 65 Compositions <280 >130° C.<40 >45 1 to 12 66 Compositions <280 >140° C. <40 >45 1 to 12 67Compositions <290 >120° C. <30 >45 1 to 12 68 Compositions <290 >130° C.<30 >45 1 to 12 69 Compositions <290 >140° C. <30 >45 1 to 12 70Compositions <285 >120° C. <30 >45 1 to 12 71 Compositions <285 >130° C.<30 >45 1 to 12 72 Compositions <285 >140° C. <30 >45 1 to 12 73Compositions <280 >120° C. <30 >45 1 to 12 74 Compositions <280 >130° C.<30 >45 1 to 12 75 Compositions <280 >140° C. <30 >45 1 to 12 76Compositions <290 >120° C. <40 >50 1 to 12 77 Compositions <290 >130° C.<40 >50 1 to 12 78 Compositions <290 >140° C. <40 >50 1 to 12 79Compositions <285 >120° C. <40 >50 1 to 12 80 Compositions <285 >130° C.<40 >50 1 to 12 81 Compositions <285 >140° C. <40 >50 1 to 12 82Compositions <280 >120° C. <40 >50 1 to 12 83 Compositions <280 >130° C.<40 >50 1 to 12 84 Compositions <280 >140° C. <40 >50 1 to 12 85Compositions <290 >120° C. <30 >50 1 to 12 86 Compositions <290 >130° C.<30 >50 1 to 12 87 Compositions <290 >140° C. <30 >50 1 to 12 88Compositions <285 >120° C. <30 >50 1 to 12 89 Compositions <285 >130° C.<30 >50 1 to 12 90 Compositions <285 >140° C. <30 >50 1 to 12 91Compositions <280 >120° C. <30 >50 1 to 12 92 Compositions <280 >130° C.<30 >50 1 to 12 93 Compositions <280 >140° C. <30 >50 1 to 12

In one advantageous embodiment, the present invention relates to acomposition as defined above, characterized in that the BAC is 1,3-BAC.

Advantageously, the 1,3-BAC is a mixture of cis and trans isomers in arespective proportion of from 0/100 to 100/0, in particular from 75/25to 25/75.

Advantageously, the proportion of cis-isomer in the 1,3-BAC is greaterthan 60%, preferentially greater than 70%, in particular greater than80%, in particular greater than 90%.

In one advantageous embodiment, the present invention relates to acomposition as defined above, in which the BAC is 1,3-BAC, and XT ischosen from 9T, 10T, 11T and 12T, more preferentially 10T, 11T and 12T.

Advantageously, XT is 10T, 10 corresponding to 1,10-decanediamine.

In one advantageous embodiment, the present invention relates to acomposition as defined above, in which the sum of the monomers whichreplace the terephthalic acid, the BAC and X is equal to 0. In thelatter embodiment, there is consequently no longer any possiblereplacement of the monomers in compositions 1 to 93 as defined above.

In one advantageous embodiment, the present invention relates to acomposition as defined above, characterized in that saidsemi-crystalline polyamide polymer is a non-reactive compositionaccording to b).

This means that said composition is the same as that of the matrix(polyamide) polymer of said thermoplastic material, since there is anabsence of reaction in this composition, which remains stable andunchanging in terms of molecular weight when it is heated for theprocessing of the thermoplastic material of the invention. Thecharacteristics of the polyamide polymer in this composition are thesame, with Mp, Tg, Mp−Tc and Delta Hc as already defined above, as thoseof the final polymer.

The polyamides according to b) are obtained by a conventionalpolycondensation reaction from the monomer components which arediamines, diacids and optionally amino acids or lactams, in particularin the context of replacement of the monomers.

In one advantageous embodiment, the present invention relates to acomposition as defined above, characterized in that said polyamidecomposition is a reactive composition of prepolymer according to a) andprecursor of said polyamide polymer of said matrix of the thermoplasticmaterial.

According to the reactive composition a), it is possible to distinguishthree possibilities given in detail below:

Advantageously, said composition a) comprises or consists of at leastone reactive prepolymer carrying, on the same chain, two end functionsX′ and Y′ which are respectively coreactive with one another bycondensation, with X′ and Y′ being amine and carboxyl or carboxyl andamine respectively.

The prepolymer is a reactive polyamide bearing, on the same chain (thatis to say on the same prepolymer), two end functions X′ and Y′, whichfunctions are respectively coreactive with one another by condensation.

This condensation (or polycondensation) reaction can bring about theelimination of byproducts. The latter can be eliminated by preferablyworking according to a process using an open-mold technology. In thecase of a closed-mold process, a step of degassing, preferably undervacuum, the by-products eliminated by the reaction is present, in orderto prevent the formation of microbubbles of the by-products in the finalthermoplastic material, which (microbubbles) can affect the mechanicalperformance levels of said material if they are not eliminated in thisway.

After condensation, the characteristics of the final polyamide polymerobtained, in this composition, are the same, with Mp, Tg, Mp−Tc andDelta Hc as already defined above.

Advantageously, said reactive composition a) comprises at least twopolyamide prepolymers which are reactive with one another and which eachrespectively carry two identical end functions X′ or Y′, said functionX′ of a prepolymer being able to react only with said function Y′ of theother prepolymer, in particular by condensation, more particularly withX′ and Y′ being amine and carboxyl or carboxyl and amine respectively.

In the same way, this condensation (or polycondensation) reaction canbring about the elimination of by-products which can be eliminated asdefined above.

After condensation, the characteristics of the final polyamide polymerobtained, in this composition, are the same, with Mp, Tg, Mp−Tc andDelta Hc as already defined above.

Advantageously, said composition a) or precursor composition comprisesor consists of:

a1) at least one prepolymer of said thermoplastic polyamide polymer,carrying n end reactive functions X′, chosen from: —NH₂, —CO₂H and —OH,preferably NH₂ and —CO₂H, with n being from 1 to 3, preferably from 1 to2, more preferably 1 or 2, more particularly 2,

a2) at least one chain extender Y-A′-Y, with A′ being a hydrocarbonbiradical of nonpolymeric structure, carrying 2 identical end reactivefunctions Y, which are reactive by polyaddition with at least onefunction X′ of said prepolymer a1), preferably with a molecular weightof less than 500 and more preferably of less than 400.

Mention may be made, as suitable examples of extenders a2) as a functionof the functions X′ carried by said semi-crystalline polyamideprepolymer a1), of the following:

-   -   when X′ is NH₂ or OH, preferably NH₂:    -   either the chain extender Y-A′-Y corresponds to    -   Y chosen from the groups: maleimide, optionally blocked        isocyanate, oxazinone, oxazolinone et epoxy,

and

-   -   A′ is a hydrocarbon-based spacer optionally comprising one or        more heteroatoms, and linking the functions Y with one another,        in particular A′ is a hydrocarbon-based spacer or a carbon-based        radical bearing the reactive functions or groups Y, chosen from:        -   a covalent bond between two functions (groups) Y in the case            where Y=oxazinone et oxazolinone or        -   an aliphatic hydrocarbon-based chain or an aromatic and/or            cycloaliphatic hydrocarbon-based chain, the latter two            comprising at least one optionally substituted ring of 5 or            6 carbon atoms, with optionally said aliphatic            hydrocarbon-based chain optionally having a molecular weight            of 14 to 400 g·mol⁻¹    -   or the chain extender Y-A′-Y corresponds to Y being a        caprolactam group and to A′ being able to be a carbonyl radical,        such as carbonylbiscaprolactam, or to A′ being able to be a        terephthaloyl or an isophthaloyl,    -   or said chain extender Y-A′-Y carries a cyclic anhydride group        Y, and preferably this extender is chosen from a cycloaliphatic        and/or aromatic carboxylic dianhydride and more preferably it is        chosen from: ethylenetetracarboxylic dianhydride, pyromellitic        dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride,        1,4,5,8-naphthalenetetracarboxylic dianhydride,        perylenetetracarboxylic dianhydride, 3,3′,4,4′-benzophenone        tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic        dianhydride, hexafluoroisopropylidene bisphthalic dianhydride,        9,9-bis(trifluoromethyl)xanthenetetracarboxylic dianhydride,        3,3′,4,4′-diphenylsulfone tetracarboxylic dianhydride,        bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride,        1,2,3,4-cyclopentanetetracarboxylic dianhydride,        3,3′,4,4′-diphenyl ether tetracarboxylic dianhydride or mixtures        thereof

and

-   -   when X′ is COOH:    -   said chain extender Y-A′-Y corresponds to:    -   Y chosen from the following groups: epoxy, oxazoline, oxazine,        imidazoline or aziridine, such as 1,1′-iso- or terephthaloyl        bis(2-methylaziridine),    -   A′ being a carbon-based spacer (radical) as defined above.

More particularly, when, in said extender Y-A′-Y, said function Y ischosen from oxazinone, oxazolinone, oxazine, oxazoline or imidazoline,in this case, in the chain extender represented by Y-A′-Y, A′ canrepresent an alkylene, such as —(CH₂)_(m)— with m ranging from 1 to 14and preferably from 2 to 10, or A′ can represent a cycloalkylene and/oran arylene which is substituted (alkyl) or unsubstituted, such asbenzenic arylenes, for example o-, m- or p-phenylenes, or naphthalenicarylenes, and preferably A′ is an arylene and/or a cycloalkylene.

In the case of carbonyl- or terephthaloyl- or isophthaloylbiscaprolactamas chain extender Y-A′-Y, the preferred conditions avoid the eliminationof byproduct, such as caprolactam, during said polymerization andprocessing in the molten state.

In the optional case mentioned above where Y represents a blockedisocyanate function, this blocking can be obtained by blocking agentsfor the isocyanate function, such as epsilon-caprolactam, methyl ethylketoxime, dimethylpyrazole or diethyl malonate.

Likewise, in the case where the extender is a dianhydride which reactswith a prepolymer P(X′)n where X′=NH₂, the preferred conditions preventany formation of an imide ring during the polymerization and during theprocessing in the molten state.

As examples of chain extenders comprising a reactive function Y=epoxywhich are suitable for implementing the invention, mention may be madeof optionally substituted aliphatic, cycloaliphatic or aromaticdiepoxides. As examples of aliphatic diepoxides, mention may be made ofaliphatic diol diglycidyl ethers, as aromatic diepoxides, mention may bemade of bisphenol A diglycidyl ethers such as bisphenol A diglycidylether (BADGE) and, as cycloaliphatic diepoxides, mention may be made ofcycloaliphatic diol or hydrogenated bisphenol A diglycidyl ethers. Moregenerally, as examples of diepoxides that are suitable for use accordingto the invention, mention may be made of bisphenol A diglycidyl ether(BADGE), and its (cycloaliphatic) hydrogenated derivative, bisphenol Fdiglycidyl ether, tetrabromo bisphenol A diglycidyl ether, orhydroquinone diglycidyl ether, ethylene glycol diglycidyl ether,propylene glycol diglycidyl ether, butylene glycol diglycidyl ether,neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether,1,6-hexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether,polyethylene glycol diglycidyl ether of Mn<500, polypropylene glycoldiglycidyl ether of Mn<500, polytetramethylene glycol diglycidyl etherof Mn<500, resorcinol diglycidyl ether, neopentyl glycol diglycidylether, bisphenol A polyethylene glycol diglycidyl ether of Mn<500,bisphenol A polypropylene glycol diglycidyl ether of Mn<500, diglycidylesters of a dicarboxylic acid, such as terephthalic acid glycidyl ester,or epoxidized diolefins (dienes) or fatty acids with a double epoxidizedethylenic unsaturation, diglycidyl 1,2-cyclohexanedicarboxylate, andmixtures of the diepoxides mentioned.

As examples of chain extenders bearing oxazoline or oxazine reactivefunctions Y that are suitable for the implementation of the invention,reference may be made to those described under references “A”, “B”, “C”and “D” on page 7 of application EP 0 581 642, and also to the processesfor preparing same and the modes of reaction thereof which are disclosedtherein. “A” in this document is bisoxazoline, “B” is bisoxazine, “C” is1,3-phenylenebisoxazoline and “D” is 1,4-phenylenebisoxazoline.

Reference may be made, as examples of chain extenders having animidazoline reactive function Y which are suitable for theimplementation of the invention, to those described (“A” to “F”) onpages 7 to 8 and table 1 on page 10 in the application EP 0 739 924, andalso to their processes of preparation and their modes of reaction whichare disclosed therein.

Reference may be made, as examples of chain extenders having a reactivefunction Y=oxazinone or oxazolinone which are suitable for theimplementation of the invention, to those described under references “A”to “D” on pages 7 to 8 of the application EP 0 581 641, and also totheir processes of preparation and their modes of reaction which aredisclosed therein.

Mention may be made, as examples of oxazinone (ring having 6 atoms) andoxazolinone (ring having 5 atoms) groups Y which are suitable, of thegroups Y derived from: benzoxazinone, oxazinone or oxazolinone, with asspacer A′ which can be a covalent single bond with for respectivecorresponding extenders being: bis(benzoxazinone), bisoxazinone andbisoxazolinone. A′ can also be a C₁ to C₁₄, preferably C₂ to C₁₀,alkylene but A′ is preferably an arylene and more particularly it can bea phenylene (substituted by Y in the 1,2 or 1,3 or 1,4 positions) or anaphthalene radical (disubstituted by Y) or a phthaloyl (iso- orterephthaloyl) or A′ can be a cycloalkylene.

For the Y functions such as oxazine (6-membered ring), oxazoline(5-membered ring) and imidazoline (5-membered ring), the radical A′ canbe as described above with it being possible for A′ to be a singlecovalent bond and with the respective corresponding extenders being:bisoxazine, bisoxazoline and bisimidazoline. A′ may also be a C₁ to C₁₄,preferably C₂ to C₁₀, alkylene. The radical A′ is preferably an aryleneand it can more particularly be a phenylene (substituted by Y in the 1,2or 1,3 or 1,4 positions) or a naphthalene radical (disubstituted by Y)or a phthaloyl (iso- or terephthaloyl) or A′ can be a cycloalkylene.

In the case where Y=aziridine (3-membered nitrogenous heterocycleequivalent to ethylene oxide with replacement of the ether —O— by —NH—),the radical A′ can be a phthaloyl (1,1′-iso- or terephthaloyl) with, asan example of an extender of this type,1,1′-isophthaloylbis(2-methylaziridine).

The presence of a catalyst of the reaction between said prepolymerP(X′)n and said extender Y-A′-Y at a content ranging from 0.001% to 2%,preferably from 0.01% to 0.5%, with respect to the total weight of thetwo coreactants mentioned, can accelerate the (poly)addition reactionand thus shorten the production cycle.

According to a more particular case of the choice of said extender, A′can represent an alkylene, such as —(CH₂)_(m)— with m ranging from 1 to14 and preferably from 2 to 10, or represents an alkyl-substituted orunsubstituted arylene, such as benzenic arylenes (such as o-, m- orp-phenylenes) or naphthalenic arylenes (with arylenes:naphthalenylenes). Preferably, A′ represents an arylene which may be asubstituted or unsubstituted benzenic or naphthalenic arylene.

As already specified, said chain extender (a2) has a nonpolymericstructure and preferably a molecular weight of less than or equal to500, more preferentially of less than or equal to 400.

Said reactive prepolymers of said reactive composition a), according tothe three options mentioned above, have a number-average molecularweight Mn ranging from 500 to 10 000, preferably from 1000 to 6000. Allthe weights Mn are determined by potentiometer or by NMR (Postma et al.(Polymer, 47, 1899-1911 (2006)).

It is clearly obvious that the reaction of a polyamide prepolymer with achain extender, even if it is capable of forming units other than amideunits, results in a polymer which is very predominantly made of amideunits, which therefore still corresponds to a polyamide polymer.

In the case of the reactive compositions of the invention according todefinition a), said reactive prepolymers are prepared by conventionalpolycondensation reaction between the diamine and corresponding diacidcomponents and optionally (according to the replacements) amino acid orlactam components. The prepolymers bearing amine and carboxyl functionsX′ and Y′ on the same chain can be obtained, for example, by adding acombination of monomers (amino acid, diamine, diacid) having in total anequal amount of amine and carboxyl units, but by not carrying out thereaction to complete conversion. Another route for obtaining theseprepolymers carrying an X′ function and a Y′ is, for example, bycombining a prepolymer carrying 2 identical X′=amine functions with adiacid prepolymer carrying Y′=carboxyl, with an overall molar content ofacid functions equal to that of the starting amine functions X′.

In order to obtain prepolymers functionalized with identical (amine orcarboxyl) functions on the same chain, it is sufficient to have anexcess of diamine (or of amine functions overall) in order to have amineend functions or an excess of diacid (or of carboxyl functions overall)in order to have carboxyl end functions.

In the case of a prepolymer P(X′)n with n identical functions X′, thefunctionality 1 can be obtained in the presence of a blockingmonofunctional component (monoacid or monoamine, depending on the natureof X=amine or carboxyl).

A functionality n=2 can be obtained starting from bifunctionalcomponents: diamines and diacids with excess of one to attach Xdepending on this excess.

For n=3, for example, for a prepolymer P(X′)n, the presence of atrifunctional component is necessary, for example the presence of atriamine (one mol per prepolymer chain) with a diamine in the reactionwith a diacid. The preferred functionality for P(X′)n is n=2.

In one advantageous embodiment, the present invention relates to acomposition as defined above, said composition a) or precursorcomposition comprising or consisting of:

a1) at least one prepolymer of said thermoplastic polyamide polymer,carrying n end reactive functions X′, and

a2) at least one chain extender Y-A′-Y,

in which X′ is NH₂ or OH, in particular NH₂, and Y is chosen from ananhydride, in particular 3,3′,4,4′-benzophenone tetracarboxylicdianhydride, an oxazinone, an oxazolinone and an epoxy.

In one advantageous embodiment, the present invention relates to acomposition as defined above, said composition a) or precursorcomposition comprising or consisting of:

a1) at least one prepolymer of said thermoplastic polyamide polymer,carrying n end reactive functions X′, and

a2) at least one chain extender Y-A′-Y,

in which X′ is CO₂H and Y is chosen from an epoxy and an oxazoline.

Advantageously, X′ is CO₂H and Y-A′-Y is chosen fromphenylenebisoxazolines, preferably 1,3-phenylenebis(2-oxazoline) or1,4-phenylenebis(2-oxazoline) (PBO).

In one advantageous embodiment, the present invention relates to acomposition as defined above, characterized in that it comprises a1) atleast one amino prepolymer (bearing —NH₂) of said thermoplastic polymerof the matrix, in particular with at least 50% and more particularlywith 100% of the end groups of said prepolymer a1) being primary aminefunctions —NH₂, and a2) at least one non-polymeric chain extenderbearing a cyclic carboxylic anhydride group, preferably borne by anaromatic ring, having as substituent a group comprising an ethylenic oracetylenic unsaturation, preferably acetylenic unsaturation, saidcarboxylic anhydride group possibly being in acid, ester, amide or imideform with said extender a2) being present in a content corresponding toan a2)/(—NH₂) molar ratio of less than 0.36, preferably ranging from 0.1to 0.35, more preferentially ranging from 0.15 to 0.35 and even morepreferentially ranging from 0.15 to 0.31, and in that said thermoplasticpolymer of the matrix is the product of the polymerization reaction byextension of said prepolymer a1) by said extender a2).

Said reaction, through the choice of the components a1) and a2) and ofthe specific molar ratio thereof, results in a final thermoplasticpolymer which is not crosslinked.

Said prepolymer a1) bears primary amine groups represented by —NH₂. Moreparticularly, it should be noted that the average number of primaryamine groups per molecule of prepolymer a1), in other words the averagefunctionality with respect to primary amine groups, can range from 1 to3 and preferably from 1 to 2. In particular, the functionality of saidprepolymer a1) of at least 50% of the end groups of said prepolymer a1)being —NH₂ primary amine functions, this means that it is possible for aportion to be carboxyl groups or blocked chain ends without a reactivegroup and, in this case, the average —NH₂ functionality can thus rangefrom 1 to 3 and preferably from 1 to 2.

The term “thermoplastic” in the case of the present invention means thatthe polymer resulting from the reaction of the prepolymer a1) and of theextender a2) is essentially thermoplastic, which means that it containsless than 15% of its weight, preferably less than 10% of its weight andmore preferentially less than 5% of its weight and even morepreferentially 0% of its weight (to within 0.5% or to within 1%), ofcrosslinked polymers which are insoluble or infusible.

Said extender a2) can be chosen from:

-   -   ethynyl o-phthalic, methylethynyl o-phthalic, phenylethynyl        o-phthalic, naphthylethynyl o-phthalic, 4-(o-phthaloylethynyl)        o-phthalic or 4-(phenyl ethynyl ketone) o-phthalic, the latter        also being called 4-(phenylethynyl) trimellitic, anhydrides and        anhydride derivatives in acid, ester, amide or imide form,    -   ethynyl isophthalic, methylethynyl isophthalic, phenylethynyl        isophthalic, naphthylethynyl isophthalic, 4-(o-phthaloylethynyl)        isophthalic, 4-(phenyl ethynyl ketone) isophthalic, ethynyl        terephthalic, methylethynyl terephthalic, phenylethynyl        terephthalic, naphthylethynyl terephthalic,        4-(o-phthaloylethynyl) terephthalic, ethynyl benzoic,        methylethynyl benzoic, phenylethynyl benzoic, naphthylethynyl        benzoic or 4-(o-phthaloylethynyl) benzoic acids or acid esters        or amides.

Advantageously, said extender a2) is chosen from aromatic anhydridecompounds, preferably o-phthalic anhydride compounds, substituted, inposition 4 of the aromatic ring, by a substituent defined by a groupR—C≡C—(R′)x- with R being a C₁-C₂ alkyl or H or aryl, in particularphenyl, or R is the residue of an aromatic carboxylic anhydride,preferably o-phthalic anhydride, bonded to the acetylenic triple bondvia the carbon in position 4 of the aromatic ring and x being equal to 0or to 1, and when x is equal to 1, R′ is a carbonyl group.

Advantageously, said extender a2) is chosen from o-phthalic aromaticanhydride compounds bearing, in position 4, a substituent group chosenfrom methylethynyl, phenylethynyl, 4-(o-phthaloyl)ethynyl or phenylethynyl ketone, also called (phenylethynyl) trimellitic anhydride, andpreferably bearing, in position 4, a substituent group chosen frommethylethynyl and phenyl ethynyl ketone.

Advantageously, said extender a2), as defined above and regardless ofits structure, has a molecular weight of less than or equal to 500,preferably less than or equal to 400.

Advantageously, the content of said extender a2), as defined above andregardless of its structure, in said polyamide polymer ranges from 1% to20%, in particular from 5% to 20%.

In one advantageous embodiment, the present invention relates to acomposition as defined above, characterized in that it is a moldingcomposition.

According to another aspect, the present invention relates to a processfor manufacturing a thermoplastic composite material, in particular amechanical part or a structural part based on said material, having acomposition as defined above, characterized in that it comprises atleast one step of polymerization of at least one reactive composition a)as defined above according to the invention or a step of molding or ofprocessing at least one nonreactive composition b) as defined above byextrusion, injection-molding or molding.

In one advantageous embodiment, the present invention relates to aprocess for manufacturing a thermoplastic material as defined above,characterized in that it comprises the following steps:

i) injection of a composition as defined above devoid of fibrousreinforcement in an open or closed mold or out of mold,

ii) polymerization reaction in the case of a reactive composition a) ofpolyamide as defined above, by heating said composition of stage i) withchain extension, as the case may be, by a polycondensation reaction orby a bulk melt polyaddition reaction, with, in the case of thepolycondensation, removal under vacuum of the condensation products whena closed mold is involved, using a vacuum extraction system, otherwiseand preferably with the polycondensation being carried out in an openmold or out of mold,

iii) processing or molding of said composition of stage i), in the caseof a nonreactive polyamide composition b), in order to form the finalpart in a mold or with another processing system, and, in the case of areactive composition a), a stage of processing by molding or by anotherprocessing system and simultaneously with polymerization stage ii).

According to another aspect, the present invention relates to asemi-crystalline polyamide polymer, characterized in that it correspondsto (or is) the polymer of the thermoplastic matrix of said thermoplasticcomposite material, as defined above, said polymer being a non-reactivepolymer as defined according to said composition b) or a polymer thatcan be obtained from a reactive composition as defined according to saidcomposition a).

This thermoplastic polymer is by definition one of the essentialcomponents of the composition of the thermoplastic material of thepresent invention and is therefore part of the invention as a productlinked to the present invention with the same common inventive conceptin the face of the same technical problem to be solved. The inventiontherefore also covers the use of said thermoplastic polymer according tothe invention as thermoplastic matrix of a thermoplastic material basedon a fibrous reinforcement as described above.

According to yet another aspect, the present invention relates to theuse of a composition as defined above or of a non-reactive polymer asdefined according to said composition b) or a polymer that can beobtained from a reactive composition as defined according to saidcomposition a), for manufacturing mechanical or structural parts, basedon said thermoplastic material, of a monolayer or multilayer tube, or ofa film.

In one advantageous embodiment, the present invention relates to the useas defined above, characterized in that said mechanical or structuralparts of said thermoplastic material concern applications in the motorvehicle, railway, marine (maritime) and wind power fields, thephotovoltaic field, the solar energy field, including solar panels andcomponents of solar power stations, the sport field, the aeronauticaland aerospace field, and the road transport (regarding trucks),construction, civil engineering, panel and leisure fields.

In another advantageous embodiment, the present invention relates to theuse as defined above, characterized in that said mechanical parts forapplications in the motor vehicle field are parts under an engine hoodfor the transportation of fluid, in particular in air intake devices,cooling devices (for example using air, cooling fluid, etc.), devicesfor the transportation or transfer of fuels or fluids, in particularoil, water, etc.

In yet another advantageous embodiment, the present invention relates tothe use as defined above, characterized in that said mechanical orstructural parts for applications in the electrical or electronics fieldare electrical and electronic goods, such as encapsulated solenoids,pumps, telephones, computers, printers, fax machines, modems, monitors,remote controls, cameras, circuit breakers, electric cable sheaths,optical fibers, switches, multimedia systems.

According to another aspect, the present invention relates to athermoplastic material resulting from the use of at least onecomposition for thermoplastic material as defined above.

According to another aspect, the present invention relates to amechanical or structural part made from thermoplastic material,resulting from the use of at least one composition as defined above orfrom the use of a polyamide polymer as defined above, or that it isbased on a composite material as defined above or that it is obtained bymeans of a process as defined above.

In one advantageous embodiment, the part defined above is a mechanicalpart for applications in the motor vehicle field, such as parts under anengine hood for the transportation of fluid, in particular in air intakedevices, cooling devices (for example using air, cooling fluid, etc.),devices for the transportation or transfer of fuels or fluids (such asoil, water, etc.).

In one advantageous embodiment, the part as defined above is amechanical or structural part for applications in the electrical orelectronics field, such as electrical and electronic goods, such asencapsulated solenoids, pumps, telephones, computers, printers, faxmachines, modems, monitors, remote controls, cameras, circuit breakers,electric cable sheaths, optical fibers, switches, multimedia systems.

Methods for Determining the Characteristics Mentioned

-   -   The measurement of the intrinsic or inherent viscosity is        carried out in m-cresol. The method is well known to those        skilled in the art. The standard ISO 307:2007 is followed but        with the solvent being changed (use of m-cresol instead of        sulfuric acid and the temperature being 20° C.).    -   The glass transition temperature Tg is measured using a        differential scanning calorimeter (DSC), after a second heating        cycle, according to the standard ISO 11357-2:2013. The heating        and cooling rate is 20° C./min.    -   The melting point Mp and the crystallization temperature Tc are        measured by DSC, according to the standard ISO 11357-3:2013. The        heating and cooling rate is 20° C./min.    -   The heat of crystallization of said matrix polymer is measured        by differential scanning calorimetry (DSC) according to the        standard ISO 11357-3:2013.    -   The modulus E′ at 180° C. is obtained from curves of dynamic        mechanical analysis (DMA) carried out on bars in tension mode,        using a temperature gradient of 2° C./min, a frequency of 1 Hz        and an amplitude of 10 μm.    -   The Mn of the prepolymer is determined by titration (assay) of        the COOH or NH₂ end functions according to a potentiometric        method and from a theoretical functionality of 2.

DESCRIPTION OF THE FIGURES

FIG. 1 shows the Mp, Tg, Tc and Deltac Hc curves obtained as a functionof the molar percentage of BACT in a BACT/10T copolyamide.

The curves represent:

Solid circles: Mp.

Empty circles: Tc.

Squares: Tg

Diamonds: Heat of crystallization.

EXAMPLES

A—Preparation of a Polyamide Polymer by the Direct Route (without ChainExtension)

The following procedure is an example of a preparation process, and isnot limiting. It is representative of all the compositions according tothe invention:

5 kg of the following starting materials are introduced into a 14-literautoclave reactor:

-   -   500 g of water,    -   the diamines,    -   the amino acid (optionally),    -   the terephthalic acid and optionally one or more other        diacid(s),    -   the monofunctional chain regulator: benzoic acid, in an amount        suitable for the targeted Mn and varying (benzoic acid) from 50        to 100 g,    -   35 g of sodium hypophosphite in solution,    -   0.1 g of a Wacker AK1000 antifoaming agent (Wacker Silicones).

The natures and molar ratios of the molecular structures and units ofthe polyamides (by referenced test) are given in table III below.

The closed reactor is purged of its residual oxygen and then heated to atemperature of 230° C. with respect to the material introduced. Afterstirring for 30 minutes under these conditions, the pressurized vaporwhich has formed in the reactor is gradually reduced in pressure over 60minutes, while gradually increasing the internal temperature so that itbecomes established at Mp +10° C. at atmospheric pressure.

The polymerization is then continued under nitrogen flushing of 20 l/huntil the targeted weight Mn shown in the characteristics table isobtained.

The polymer is subsequently emptied out via the bottom valve, thencooled in a water trough and then granulated.

The results are given in the following tables III-VI. They were obtainedusing 1,3-BAC having a cis/trans ratio of 75/25 mol %.

TABLE III Inherent 10T BACT

p

c

p − Tc DeltaHc

g viscosity

′ 180° C. Ref

ol %

ol % ° C. ° C. ° C. J/g ° C. —

Pa C 10T* 100.0 0.0 314 279 35 63 120 insoluble — I1 60.0 40.0 275.6241.7 33.9 60.8 134.0 0.92 — I2 50.0 50.0 281.7 248.3 33.4 53.5 153.41.05 805.3 I3 50.0 50.0 279.4 242.5 36.9 55.5 146.0 0.93 — I4 45.0 55.0279.8 252.0 27.8 62.2 142.7 0.87 — I5 45.0 55.0 282.0 253.5 28.5 49.7160.2 1.09 — I6 40.0 60.0 286.1 250.4 35.7 57.0 163.9 0.94 886   I7 30.070.0 289.7 258.6 31.1 40.6 165.6 0.86 — C BACT* 0.0 100.0 349 — — — 187— — C denotes Comparative I denotes Invention *According to JP2015017177

indicates data missing or illegible when filed

The results of table 3 show that, for a BACT molar fraction of 20 (notindicated in the table) to 70 mol % (preferably 25 to 60 mol %), themelting point is below 290° C. (preferably below 280° C.).

At the same time, the Tg is very high and can be modulated from 125° C.(not indicated in the table) to approximately 165° C. The heat ofcrystallization for all these products is particularly high, and inparticular greater than 50 J/g (in particular greater than the MXDT/10Tdescribed in WO 2014/064375).

TABLE IV Inherent 10T BACT 11

p

c Mp − Tc DeltaHc Tg viscosity ef

ol %

ol %

ol % ° C. ° C. ° C. J/g ° C. — 8 41.5 50.8 7.7 269.2 232.4 36.8 41.4149.5 1.14 9 38.2 46.9 14.9 256.1 189.7 66.4 28.7 144.9 1.22

indicates data missing or illegible when filed

The partial replacement of one of the two units with 11-aminoundecanoicacid is also possible and gives good results for obtaining a good Mp/Tgcompromise (table IV).

TABLE V Inherent 10T BACT 6T

p

c Mp − Tc DeltaHc Tg viscosity ef

ol %

ol %

ol % ° C. ° C. ° C. J/g ° C. — 10 42.5 51.9 5.5 270.9 234.0 36.9 49.7161.3 1.02 11 40.5 49.5 10 263.9 233.2 30.7 44.5 143.2 0.86

indicates data missing or illegible when filed

The partial replacement of one of the two units with the 6T unit is alsopossible and gives good results for obtaining a good Mp/Tg compromise(table V).

TABLE VI Molecular structure/ p c p − Tc DeltaHc g Inherent ef. Testtype Molar composition C. C. C. J/g C. viscosity 1 Comparative 10T/6T(59/41) 81 36 5 44 22 1.12 (EP1988113) 2 Comparative 10T/6T/11(60/24/16) 69 20 9 39 11 1.25 (EP1988113) 3 Comparative 10T/TMDT (59/41)63 97 6 35 33 1.15 (WO2011/00393) 10T Comparative 10T (100) 14 79 5 6320 insoluble 4 Comparative 10T/11 (67/33) 69 32 7 50 4 1.19 5Comparative 10,T/11 (59/41) 61 13 6 39 8 1.15 6 Comparative 10T/10I(67/33) 69 05 4 32 10 1.12 7 Comparative MXDT/11 (59/41) 11 *) 100 12 111.25 8 Comparative MPMDT/11 (59/41) *) — 4 1.14 9 Comparative 10T/MXDT(50/50) 62 11 1 17 37 0.99 10 Comparative 10T/MPMDT (59/41) 64 19 5 4026 1.11 11 Comparative 10T/MPMDT (50/50) 45 85 0 22 27 1.12 12Comparative 10T/12T/11 (60/24/16) 71 46 5 56 05 0.98 13 Comparative18T/MXDT (71/29) 64 42 2 47 5 0.86 (*): No crystallization on cooling.

The results of table VI show that the total replacement of the Bac or ofthe 10T unit results in compositions which do not have the required Mp,Tg, Mp−Tc and delta Hc values.

B—Preparation of a Polyamide Polymer by Chain Extension of a ReactivePrepolymer (or Oligomer)

B-1 Preparation of Reactive Prepolymers of P(X′)n (or P(Y′)n) Type

The following procedure is an example of a preparation process, and isnot limiting. It is representative of all the compositions according tothe invention:

5 kg of the following starting materials are introduced into a 14-literautoclave reactor:

-   -   500 g of water,    -   the diamines,    -   the amino acid (optionally),    -   the terephthalic acid and optionally one or more other        diacid(s),    -   35 g of sodium hypophosphite in solution,    -   0.1 g of a Wacker AK1000 antifoaming agent (Wacker Silicones).

The closed reactor is purged of its residual oxygen and then heated to atemperature of 230° C. of the material. After stirring for 30 minutesunder these conditions, the pressurized vapor which has formed in thereactor is gradually reduced in pressure over 60 minutes, whilegradually increasing the internal temperature so that it becomesestablished at Mp +10° C. at atmospheric pressure.

The oligomer (prepolymer) is subsequently emptied out via the bottomvalve, then cooled in a water trough and then ground.

The natures and molar ratios of the molecular structures and units ofthe polyamides (by referenced test) are given in table VII below. Theywere obtained using 1,3-BAC having a cis/trans ratio of 75/25 mol %.

TABLE VII

ecular

and

al Inherent

tion Mp Tc Mp − Tc DeltaHc Tg viscosity Acid number

) ° C. ° C. ° C. J/g ° C. — meq/kg* n

,3- 259.2 217 42.2 45.0 121.0 0.35 713

40/60)

,3- 265.7 230.6 35.1 58.6 104.6 0.42 0

40/60) *Milliequivalents per kilogram (**) Potentiometric Mn

indicates data missing or illegible when filed

B-2 Preparation of the Polyamide Polymer by Reaction Between PrepolymerP(X′)n and P(Y′)n

A stoichiometric mixture (mol(acid)=(mol(amine)) of the two oligomers P1(X′=COOH) and P2 (Y′=NH₂) above, dried and ground, is introduced withnitrogen flushing into a DSM corotating conical screw microextruder (15ml in volume) preheated to 280° C. with screw rotation at 100 rpm. Themixture is left to recirculate in the microextruder and the increase inthe viscosity is monitored by measuring the normal force. Afterapproximately 15 minutes, the contents of the microextruder are emptiedout in the form of a rod. The air-cooled product is granulated.

The product I12 obtained has an inherent viscosity equal to 1.92.

B-3 Preparation of the Polyamide Polymer by Reaction Between PrepolymerP(X′)n and an Extender Y-A′-Y

10 g of the dried and ground oligomer P1 above are mixed with astoichiometric amount of 1,3-phenylenebisoxazoline (PBO). The mixture isintroduced under nitrogen flushing into a DSM corotating conical-screwmicroextruder (15 ml in volume) preheated to 280° C. with rotation ofthe screws at 100 rev/min. The mixture is left to recirculate in themicroextruder and the increase in the viscosity is monitored bymeasuring the normal force. After approximately 2 minutes, a plateau isreached and the contents of the microextruder are emptied out in theform of a rod. The air-cooled product is granulated.

The product I13 obtained has an inherent viscosity equal to 0.97.

1. A composition suitable for a thermoplastic material, comprising: 0 to70% by weight of short reinforcing fibers, 30% to 100% by weight of athermoplastic matrix based on at least one semi-crystalline polyamidepolymer, 0 to 50% of additives and/or other polymers, said thermoplasticmatrix comprising at least one semi-crystalline BACT/XT copolyamide inwhich: BACT is a unit comprising an amide unit present at a molarcontent ranging from 20% to 70%, wherein BAC is chosen from1,3-bis(aminomethyl)cyclohexyl (1,3-BAC), 1,4-bis(aminomethyl)cyclohexyl(1,4-BAC) and a mixture thereof, and wherein T is terephthalic acid, XTis a unit comprising an amide unit present at a molar content rangingfrom 30% to 80%, wherein X is a C9 to C18 linear aliphatic diamine, andwherein T is terephthalic acid, in the BACT and/or XT units,independently of one another, up to 30 mol %, relative to the totalamount of dicarboxylic acids, of the terephthalic acid can be replacedwith other aromatic, aliphatic or cycloaliphatic dicarboxylic acidscomprising 6 to 36 carbon atoms, and in the BACT and/or XT units,independently of one another, up to 30 mol % of the BAC and/or whereappropriate of X, relative to the total amount of diamines, can bereplaced with other diamines comprising from 4 to 36 carbon atoms and inthe copolyamide, no more than 30 mol %, relative to the total amount ofmonomers, can be formed by lactams or aminocarboxylic acids, and oncondition that the sum of the monomers which replace the terephthalicacid, the BAC and X does not exceed a concentration of 30 mol % relativeto the total amount of monomers used in the copolyamide, and oncondition that BACT and XT units are always present in said polyamidepolymer.
 2. The composition as claimed in claim 1, wherein saidsemi-crystalline polyamide polymer has a melting point Mp<290° C., asdetermined according to the standard ISO 11357-3 (2013).
 3. Thecomposition as claimed in claim 1, wherein said semi-crystallinepolyamide polymer has a glass transition temperature Tg>120° C., asdetermined according to the standard ISO 11357-2 (2013).
 4. Thecomposition as claimed in claim 1, wherein said semi-crystallinepolyamide polymer exhibits a difference between the melting point andthe crystallization temperature Mp−Tc<40° C., preferably <30° C., asdetermined according to the standard ISO 11357-3:2013.
 5. Thecomposition as claimed in claim 1, wherein the heat of crystallizationof the semi-crystalline polyamide polymer, measured by differentialscanning calorimetry (DSC) according to the standard ISO 11357-3:2013,is greater than 40 J/g.
 6. The composition as claimed in claim 1,wherein the BAC is 1,3-BAC.
 7. The composition as claimed in claim 1,wherein the BAC is 1,3-BAC, and XT is chosen from 9T, 10T, 11T and 12T.8. The composition as claimed in claim 1, wherein the XT is 10T, wherein10 corresponds to 1,10-decanediamine.
 9. The composition as claimed inclaim 1, wherein the sum of the monomers which replace the terephthalicacid, the BAC and X is equal to
 0. 10-11: (canceled)
 12. The compositionas claimed in claim 1, further comprising at least one additive.
 13. Thecomposition as claimed in claim 12, wherein the additive is chosen froman antioxidant, a heat stabilizer, a UV absorber, a light stabilizer, animpact modifier, a lubricant, an inorganic filler, a flame retardantagent, a nucleating agent and a dye.
 14. The composition as claimed inclaim 1, wherein it is a molding composition. 15-25: (canceled)
 26. Thecomposition as claimed in claim 1, which contains the short reinforcingfibers.
 27. A method of preparing the composition as claimed in claim 1,comprising combining the short reinforcing fibers if present,thermoplastic matrix, and additives and/or other polymers if present.28. A method of preparing mechanical or structural parts, comprisingproducing a mechanical or structural part from the composition asclaimed in claim
 1. 29. The method of claim 28, comprising molding thecomposition.
 30. A mechanical or structural part comprising thecomposition as claimed in claim
 1. 31. The mechanical or structural partas claimed in claim 30, which concerns an application in the motorvehicle field, electrical and electronic fields, railway field, marineand wind power fields, photovoltaic field, solar energy field, sportfield, aeronautical and aerospace fields, road transport field,construction field, civil engineering field, panel field and leisurefield.
 32. The mechanical or structural part as claimed in claim 30,which is a part under an engine hood for the transportation of fluid, acooling device, or a device for the transportation or transfer of fuelsor fluids.
 33. The mechanical or structural part as claimed in claim 30,which is an electrical or electronic good.
 34. The mechanical orstructural part as claimed in claim 30, which comprises a monolayer ormultilayer tube or a film.
 35. A composition suitable for athermoplastic material, comprising: 0 to 70% by weight of shortreinforcing fibers, 30% to 100% by weight of a thermoplastic matrix, and0 to 50% of additives and/or other polymers, wherein the thermoplasticmatrix comprises at least one reactive polyamide prepolymer whichproduces a semi-crystalline polyamide polymer when subjected topolymerization, the reactive polyamide prepolymer comprises at least oneBACT/XT copolyamide, BACT is a unit comprising an amide unit present ata molar content ranging from 20% to 70%, wherein BAC is chosen from1,3-bis(aminomethyl)cyclohexyl (1,3-BAC), 1,4-bis(aminomethyl)cyclohexyl(1,4-BAC) and mixtures thereof, and T is terephthalic acid, XT is a unitcomprising an amide unit present at a molar content ranging from 30% to80%, wherein X is a C9 to C18 linear aliphatic diamine, and T isterephthalic acid, in the BACT and/or XT units, independently of oneanother, up to 30 mol %, relative to the total amount of dicarboxylicacids, of the terephthalic acid can be replaced with other aromatic,aliphatic or cycloaliphatic dicarboxylic acids comprising 6 to 36 carbonatoms, and in the BACT and/or XT units, independently of one another, upto 30 mol % of the BAC and/or where appropriate of X, relative to thetotal amount of diamines, can be replaced with other diamines comprisingfrom 4 to 36 carbon atoms, in the BACT/XT copolyamide, no more than 30mol %, relative to the total amount of monomers, can be formed bylactams or aminocarboxylic acids, the sum of the monomers which replacethe terephthalic acid, the BAC and X does not exceed a concentration of30 mol % relative to the total amount of monomers used in the BACT/XTcopolyamide, and BACT and XT units are always present in the BACT/XTcopolyamide.
 36. The composition as claimed in claim 35, wherein saidsemi-crystalline polyamide polymer has a melting point Mp<290° C., asdetermined according to the standard ISO 11357-3 (2013).
 37. Thecomposition as claimed in claim 35, wherein said semi-crystallinepolyamide polymer has a glass transition temperature Tg>120° C., asdetermined according to the standard ISO 11357-2 (2013).
 38. Thecomposition as claimed in claim 35, wherein said semi-crystallinepolyamide polymer exhibits a difference between the melting point andthe crystallization temperature Mp−Tc<40° C., as determined according tothe standard ISO 11357-3:2013.
 39. The composition as claimed in claim35, wherein the heat of crystallization of said semi-crystallinepolyamide polymer, as measured by differential scanning calorimetry(DSC) according to the standard ISO 11357-3:2013, is greater than 40J/g.
 40. The composition as claimed in claim 35, wherein BAC is 1,3-BAC.41. The composition as claimed in claim 35, wherein BAC is 1,3-BAC, andXT is chosen from 9T, 10T, 11T and 12T.
 42. The composition as claimedin claim 35, wherein XT is 10T, and wherein 10 corresponds to1,10-decanediamine.
 43. The composition as claimed in claim 35, whereinthe sum of the monomers which replace the terephthalic acid, the BAC andX is equal to
 0. 44. The composition as claimed in claim 35, furthercomprising at least one additive.
 45. The composition as claimed inclaim 44, wherein the additive is chosen from an antioxidant, a heatstabilizer, a UV absorber, a light stabilizer, an impact modifier, alubricant, an inorganic filler, a flame retardant agent, a nucleatingagent and a dye.
 46. The composition as claimed in claim 35, which is amolding composition.
 47. The composition as claimed in claim 35, whichcontains the short reinforcing fibers.
 48. A method of preparing thecomposition as claimed in claim 35, comprising combining the shortreinforcing fibers if present, thermoplastic matrix, and additivesand/or other polymers if present.
 49. A method of preparing mechanicalor structural parts, comprising producing a mechanical or structuralpart from the composition as claimed in claim
 35. 50. The method ofclaim 49, comprising polymerizing the reactive polyamide prepolymer. 51.A mechanical or structural part comprising the composition as claimed inclaim
 35. 52. The mechanical or structural part as claimed in claim 51,which concerns an application in the motor vehicle field, electrical andelectronic fields, railway field, marine and wind power fields,photovoltaic field, solar energy field, sport field, aeronautical andaerospace fields, road transport field, construction field, civilengineering field, panel field and leisure field.
 53. The mechanical orstructural part as claimed in claim 51, which is a part under an enginehood for the transportation of fluid, a cooling device, or a device forthe transportation or transfer of fuels or fluids.
 54. The mechanical orstructural part as claimed in claim 51, which is an electrical orelectronic good.
 55. The mechanical or structural part as claimed inclaim 51, which comprises a monolayer or multilayer tube or a film.